Low interfacial tension surfactants for petroleum applications

ABSTRACT

The invention relates to a class of novel surfactants that have utility in the recovery and/or extraction of oil.

RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.12/481,072 filed Jun. 9, 2009, which claims the benefit of U.S.Provisional Application No. 61/060,004 filed Jun. 9, 2008. The entireteachings of the above applications are incorporated herein byreference.

FIELD OF THE APPLICATION

The application relates generally to surfactants useful for petroleumapplications.

BACKGROUND

A number of problems in the petroleum industry derive from theviscosity, surface tension, hydrophobicity and density of crude oil.Heavy crude oil in particular, having an API gravity of less than 20degrees, is difficult to transport due to its viscosity, and isdifficult to remove from surfaces to which it has adsorbed, due to itshydrophobicity and immiscibility with water. Extra-heavy crude oil orbitumen, having an API gravity of less than 10 degrees, is heavier thanwater, so that it can sink to the bottom of a water formation, causingsub-surface contamination.

The properties of crude oil contribute to the limitations of oilrecovery from traditional oil fields. Conservative estimates suggestthat 30% of the technically recoverable oil in U.S. oil fields isinaccessible due to the adsorption of the residual oil to porousgeologies. Technologies to unlock the oil in these so-called “dead”wells presently involve the use of hot water injections with expensivesurfactants, chemistries that are applied to overcome the hydrophobicityof the adsorbed oil so that it can be mobilized.

The properties of crude oil also contribute to the difficulty ofenvironmental remediation following, for example, an oil spill onto abody of water. The high interfacial tension causes the oil to float onthe water and adhere to plants, animals and soil. As the aromaticconstituents of the oil evaporate, the heavier residues can sink,contaminating the subsurface structures. Current treatment of spilledoil on water surfaces relies on time-consuming and expensive biologicaldegradation of the oil. Thick, adherent crude oil cause environmentalproblems in the oil fields as well. Oil deposits attached to vehiclesand equipment must be cleansed with jets of hot water and caustics.

The viscosity of heavy crude oil makes the substance difficult andexpensive to transport to upgrading facilities. Because of itsviscosity, a significant amount of energy is required to pump it throughpipelines to a refinery. Furthermore, the viscosity affects the speed atwhich the heavy crude oil can be pumped, decreasing the overallproductivity of an oil field. Exploiting certain oil fields or other oildeposits may be economically unfeasible to develop at present because ofthe transportation-related costs.

Surfactants have been widely used in the petroleum industry toameliorate the effects of crude oil's physical properties. Surfactantmolecules consist of hydrophobic and hydrophilic parts. Theiramphiphilic nature allows them to be adsorbed at an oil/water interface,forming micelles that allow the interfacial tension between oil andwater to be reduced.

Surfactants are sometimes used for desalting of crude oil. Desaltingrefers to the process of removing salts from oil, making the oil moresuitable for further refining. The salts are typically dissolved inwater that is associated with oil, so the removal of water has multiplebenefits. The presence of water reduces the energy content of oil, andit carries salts that can harm catalyst performance or cause corrosion.Ethoxylated nonylphenols have been used for desalting of crude oil, butthese compounds pose hazards to the environment.

Furthermore, surfactant technologies for the aforesaid petroleumapplications typically are expensive or must be used at highconcentrations. Additionally, demulsification can prove to be difficult,as these surfactants are designed for emulsifying purposes.Demulsification typically requires added materials and steps to break upthe emulsion, which increases the effective cost of use. Furthermore,the salts present in nature can inactivate many surfactant technologies.In addition, other surfactant technologies for petroleum applicationsare tailored only to oils of a limited composition.

The development of a technology that can provide emulsion and favorabletransport properties while maintaining the ability to demulsify ondemand, all under variable conditions of salinity, remains unmet in theart. Such a technology would have wide reaching impact across theoilfield chemical sector in applications such as those mentioned above,particularly if the material could be inexpensively produced and couldbe applied to a variety of oil types.

SUMMARY

The invention relates to the discovery that novel surfactants have goodto excellent properties in recovering or extracting oil, such as fossilfuels. Accordingly, in some embodiments, the invention relates to acompound having the formula I:

wherein Ar is a substituted or unsubstituted aryl, aralkyl (e.g.,benzyl) or heteroaryl group; in some embodiments, Ar is a substituted orunsubstituted aryl, heteroaryl group, preferably a substituted orunsubstituted phenyl group;p is 1 or 2, preferably 2;m and n are independently 0, 1, 2, 3, 4, or 5, preferably 1;each of G₁ and G₂ are independently absent, O, S, NR₂, (CO)O, O(CO), CO,CONR₂, orNR₂CO; preferably each G₁ and G₂ are independently O or C(O)O;each R₂ is independently H or a lower alkyl; in some embodiments, thelower alkyl is a C1 to C5 alkyl;each G₃ is independently absent, (CH₂)_(q) or G₁;q is 1, 2, 3, 4 or 5;R is a hydrophilic group; preferably the hydrophilic group is COOH, or ahydrophilic polymer, such as a polyethylene glycol or apolypropyleneoxide;R₁ is a saturated or unsaturated hydrophobic aliphatic group; in someembodiments, R₁ is C₅ to C₁₈ alkyl, alkenyl or alkadienyl, preferably astraight chain C₅ to C₁₈ alkyl;wherein, when p is 1, Ar is substituted by one or more of OR₂, SR₂ andN(R₂)₂; preferably, when p is 1 Ar is substituted by OH, SH or NH₂.

In one preferred embodiment, G₁ is C(O)O, G₂ is absent and n is 0.Alternatively, where G₁ is O, G₂ is not absent, and is preferably O or(CO)O.

A particularly preferred surfactant is a compound having the formula(II):

wherein R₅ is a hydrophilic group; andR₄ is a saturated or unsaturated hydrophobic aliphatic group.

The invention further relates to a compound having formula III:

wherein G₁ is selected from the group consisting of S, NR₂, (CO)O,O(CO), CO, CONR₂, and NR₂CO; preferably G1 is C(O)O;each R₂ is independently H or a lower alkyl;wherein, R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ are each independently, H, OH,halogen, C₁₋₅ alkyl, C₁-C₅ alkoxy, a C₃-C₇-cycloalkyl group, a phenylgroup optionally substituted by hydroxyl, halogen, lower alkyl or loweralkoxy, or Fragment I having the formula shown below:

wherein R₁, m and G₁ are as defined above;wherein at least one of R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ is Fragment I or OH;or a salt thereof.

A particularly preferred surfactant is a compound having the formula IV:

wherein m and R₁ are as defined above.

Preferred compounds of formula IV are compounds wherein m is 1 and R₁ isa straight chain C₅ to C₁₈ alkyl.

The invention further relates to a method for extracting oil from an oilmixture comprising:

(a) adding a compound of Formula I to an oil mixture, and

(b) collecting the oil.

The oil mixture may comprise oil sands, waterborne oil slicks or oildeposits. Further, the method can comprise the additional steps ofadding water or transporting the mixture via a pipeline. In anotherembodiment, the compounds of the invention can be used in methods ofdegreasing machinery, such as those used in oil or bitumen production.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates examples of critical micelle concentration ofcompounds of formulas shown below, termed R1 and R2, on the graphsbelow.

FIG. 2 shows a plot of CMC as a function of pH for two molecules, R1 andR2.

FIG. 3 compares the capabilities of the R1 and R2 surfactants inemulsifying and transporting heavy crude oils, measuring the viscosityof diluted bitumen.

DETAILED DESCRIPTION General Formulations

Disclosed herein are compositions, systems and methods related toultra-low interfacial tension (“IFT”) surfactants for applications inthe petroleum industry. In certain embodiments, the present disclosureis based on the discovery that certain resorcinol-based estersurfactants are highly effective surfactants for petroleum applications,and can be used as additives in petroleum processing, oil sandsextraction and processing, environmental remediation, enhanced oilrecovery, and the like. In one embodiment, compositions of particularuse in these systems and methods can include at least one compound ofthe formula (V):

wherein R₁ is a hydrophobic group as defined above.

In alternate embodiments, compositions of particular use in thesesystems and methods can include at least one compound of formula (VI):

In one embodiment, compositions of particular use in these systems andmethods can include at least one compound of the formula (VII):

wherein R₆ and R₇ are each independently a hydrophobic group and R₁ isas defined above.

The compounds described herein can be used as surfactants. The inventivesurfactant compounds comprise an aromatic core with pendant aliphatichydrophobic and hydrophilic portions. As will be understood by one ofskill in the art the hydrophobic portion of the surfactant compound cancomprise one or more hydrophobic groups or substituents. Similarly, thehydrophilic portion of the inventive compounds can comprise one or morehydrophilic groups or substituents. Attached aliphatic hydrophobicportions or groups can consist of linear or branched, saturated orunsaturated, substituted or unsubstituted higher alkyls. For example,the hydrophobic group can be derived from alkanes with or withoutinternal or terminal alkenes. In some embodiments, the higher alkylcomprises at least five carbon atoms. In other embodiments, the higheralkyl is a C₅ to C₁₈ alkyl, alkenyl or alkadienyl. Hydrophilic portionsor groups can be an ionizable groups, including, for example, amines andcarboxylic acids. Hydrophilic groups also include hydrophilic polymers,including, but not limited to, polyalkylamine, poly(ethylene glycol) orpoly(propylene glycol). Nonionic hydrophilic materials such aspolyalkylamine, poly(ethylene glycol) or poly(propylene glycol) can beused to increase hydrophilicity or aid stability in salt solutions.

In some embodiments, the aliphatic groups include saturated orunsaturated carbon chains, preferably between five and eighteen units inlength, or hydrogen. The carbon chains can optionally be unsaturatedand, when present, reside anywhere along the carbon chain.

The aromatic core can be carbocyclic or heterocyclic, monocyclic orpolycyclic, substituted or unsubtstituted. Preferred aryl groups can bederived from resorcinol, phenol, creosol, benzyl alcohol, naphthalene,anthracene, pyrene, tetrahydronaphthyl, indanyl, idenyl and the like.Heteroaromatic structures such as thiophene, selenophene, silole,pyrrole, pyridine, furan, imidazole, indole, pyrazinyl, pyrimidinyl,pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl,oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzimidazolyl,benzooxazolyl, quinoxalinyl, and the like can also be used as thearomatic core. The term “substituted” refers to substitution byindependent replacement of one or more of the hydrogen atoms thereonwith substituents including, but not limited to, —OH, —NH₂,—NH—C₁-C₁₂-alkyl, —O—C₁-C₁₂-alkyl, —SH, and —S—C₁-C₁₂-alkyl.

In certain aspects of the invention, the hydrophilic portion ofcompounds of the invention is one or more ionizable carboxylic acidgroups, which groups make up the totality of the hydrophilic portion. Bythemselves, the carboxylic acid portions are not enough to effectivelystabilize emulsions formed by the mixture of a waterborne suspension ofthe disclosed surfactant compounds. Addition of a small amount of base(greater than pH 8) is sufficient to ionize, leaving a more active,emulsion-forming material. The emulsion can later be destabilized byadding acid to the material, removing the charge stabilization andsplitting the two incompatible phases.

Changing pH is one method to enabling and disabling the surfactantbehavior; however, compounds of formula (I) and formula (III) aretypically unstable hydrolytically. For example, in certain embodiments,exposure to base for prolonged periods of time will degrade thecompounds of formula (I) and formula (III) to resorcinol and alkylatedsuccinic acid. The decomposition byproducts have little to no surfactantbehavior, and thus can be utilized as another means to destabilize theformed emulsion. The disintegration follows a predictable profile whichcan be exploited for tunable, time-based demulsion.

This behavior has utility for petroleum-related applications. If oneknows, for example, the residence time of oil in a pipeline, the amountof base can be precisely calculated and added to cause decompositionbegin in the pipeline and separation to occur immediately after theemulsion reaches its destination. This has the benefit of decreasingresidence time in a storage facility while the emulsion breaks.

Applications

Environmental Remediation

By taking advantage of the low IFT behavior of the surfactant familiesdisclosed herein, such surfactants may be suitable for applicationswhere undesired petroleum products pose an environmental problem. Oilcleanup using surfactants may be required for two different types ofcontamination. First, as an oil slick dispersant, the surfactant familycan be used on waterborne slicks, acting as a dispersing agent. It willact to disperse the oil into the water body itself and encouragebiodegradation through natural decomposition means. Additionally, asolution of surfactant can be used to remove physisorbed crude orrefined oils from inorganic rocks, sand, or other substrates as anemulsion.

Oil Sands Extraction

Oil sands comprise heavy petroleum products coating sand and clay, anassemblage that is similar to certain artificial composites that areformed during a man-made oil spill, as described above. The systems andmethods described herein may be useful for extracting bitumen from theother components of the tar sands material. Currently, mined oil sandsare extracted using hot water, a process that causes the less densebitumen to flow off the sand and float to the surface of a settlingtank. This so-called “primary froth” is contaminated with variousmaterials derived from the mined products (solid particles, clay, andsand). Current froth treatment utilizes naphtha, a valuable fraction ofpurified petroleum, to dilute the bitumen and decrease the viscosity tothe point of flowability. This allows solids and water to be removed bysettling and centrifugation methods. By using an aqueous solution ofsurfactant as the dilution medium instead of naphtha, the latter solventcan be replaced with water and surfactant, thus decreasing the cost ofpurifying the froth. Additionally, when the surfactant-diluted bitumenis recovered from the water, the hydrophilic portions associated withthe froth (clay, water, salts) will preferentially partition to thewater phase and be separable from the bitumen.

Use of surfactants in accordance with these systems and methods mayfurther be applied to other aspects of the extraction process, forexample in the oil sands strip mining or in-situ operations, where theability to emulsify the petroleum component of the oil sands ore mayenhance the efficiency or economy of separating the bitumen from theinsoluble byproducts.

Oil Field Transport Emulsions

Transporting petroleum precursors for further processing is a necessary,though expensive, part of obtaining usable crude oil. When petroleum isobtained as a heavy crude, it needs to be transported to an upgradingfacility for conversion to useful petroleum products. Typically,pipeline transport is the most economical means to accomplish this. Whenoil sands are used as precursors in the production of synthetic crudeoil, they are transported for further processing after extraction andfroth treatment through pipelines as a naphtha-diluted bitumen so thatthey can undergo further upgrading processes, including cracking andcoking, amongst other standard refining operations. For these types ofapplications in the petroleum and tar sands industries, the heavy oil oroil precursor materials (respectively) may be transported throughpipelines as oil-in-water mixtures or emulsions. It is understood thatmore viscous matter being sent through pipelines has a greaterresistance to flow and consequently requires more energy to move anequivalent distance. Hence, decreasing the viscosity of the flowablematter decreases the amount of pumping energy required, and potentiallyimproves the transit time and the productivity of the overall process.Mixing water with crude oil or bitumen can decrease the viscosity ofthese latter substances towards the viscosity of water, but only if awater-continuous emulsion is created. The described low IFT surfactantscan compatibilize oil and water into an emulsion that can be pumped withgreatly decreased energy requirements and/or increase the throughput ofcrude oil or oil precursors to their destinations.

Auxiliary Petroleum Applications

There also exist many other opportunities in the oilfield chemicalsector for degreasing applications, as can be accomplished with thesystems and methods disclosed herein. Periodically, machinery used inoil and bitumen production must be cleaned for maintenance andperformance reasons. With petroleum production heading towards heaviercrude reserves, the need for an effective degreaser becomes even moreacute: exposure to heavier crude oils results in thicker, more adherentoil residues that must be removed during the cleaning/degreasingprocesses. The described low IFT surfactants can be an active ingredientin an industrial degreasing formulation for these purposes.

Enhanced Oil Recovery (EOR)

Tertiary oil recovery, also known as “enhanced” or “improved” oilrecovery, makes use of low IFT polymers to produce oil from wells thathave stopped producing of their own accord. Injection of a low IFTsurfactant into one of these less productive wells can stimulateproduction from the residual oil left adhered to the surface of porousrocks. Compounds produced according to these systems and methods areuseful as low IFT surfactants for EOR. Due to the temperatures andresidence time underground, certain esters made in accordance withformula (I) or formula (II) may be too unstable for these applications.In addition, the resident acid groups on the compound of formula (II)are highly sensitive to saline commonly found in well formations.

The compound of formula (III) may be particularly suitable for EORapplications:

R₄ and R₅ are as defined above.

In some embodiments, R₄ can include a linear or branched carbon chainconsisting of five to eighteen carbon atoms. Advantageously, substituentR₄ can be a saturated or unsaturated carbon chain consisting of five toeighteen carbon atoms.

In some embodiments, R₅ can include water soluble oligomers such aspoly(ethylene glycol) or polypropylene oxide). By using a smallpoly(ethylene glycol) as the hydrophilic portion the substituent R₅, andall ether connectivity, the molecule of formula (II) may desirablywithstand the temperature and salinities found underground for therequisite time period.

Desalting

Desalting refers to the process of removing salts from oil, making theoil more suitable for further refining. Salts, including magnesiumchloride, sodium chloride and calcium chloride can be found in crudeoil. If allowed to remain in the crude oil during the refineryoperation, the salts can dissociate and the chloride ion can ionize toform hydrochloric acid, which, along with various organic acids found incrude oil, contributes to corrosion in refinery equipment. In addition,other metal salts (e.g., potassium, nickel, vanadium, copper, iron andzinc) can be found in the crude oil, also contributing to fouling of theequipment and end-product degradation. Crude oil also containsemulsified water, which contains dissolved salts.

Desalting crude oil takes advantage of the fact that the salts dissolvein a water phase, which is separable from the oil phase. Crude oilnaturally contains water in emulsion, as mentioned above. For certaintechniques of desalting, additional water may be added to the oil (e.g.,in an amount between 5-10% by volume of crude) so that the impuritiescan further dissolve in the water. The water-in-oil emulsion can bebroken with the assistance of emulsion-breaking chemicals and/or byexposing the emulsion to an electrical field that polarizes the waterphase, so that the water phase bearing the impurities separates from thepetroleum phase. Ethoxylated nonylphenols are a class of nonionicsurfactants that have been used for desalting crude oil according tothese principles.

The surfactant families disclosed herein can facilitate thedemulsification of the water-in-oil emulsion, so that the oil phaseseparates from the water phase, with the water phase carrying thesoluble impurities (i.e., the salts). In embodiments, the hydrophilicportion of the surfactant compound can include one or more ionizablecarboxylic acid groups that can be ionized at a basic pH (e.g., >8) toproduce an emulsion-sustaining material. To destabilize the emulsion,acid may be added, removing the charge stabilization and allowing thetwo phases to segregate from each other.

EXAMPLES Example 1 Synthesis of Compounds of Formula (I)

Compounds having the structure of formula (I) may be synthesized asfollows:

A 300 ml bomb is charged with resorcinol (5 g, 48 mmol) and Eka SA 210brand alkylated succinic anhydride (100% C18 chain, 16.8 g., 48 mmol).To this, acetone (150 ml) is added, the vessel is sealed and heated to80° C. for 16 hours. After the reaction is complete, acetone is removedin vacuo and the remaining amber oil is collected in quantitative yield.The scheme below illustrates this Synthesis I.

Example 2 Synthesis of Compounds of Formula (II)

Compounds having the structure of formula (II) may be synthesized asfollows:

A 300 ml bomb is charged with resorcinol (5 g, 48 mmol) and Eka SA 210brand alkylated succinic anhydride (100% C₁₈ chain, 33.7 g, 96 mmol). Tothis, acetone (150 ml) is added, the vessel sealed, and heated to 80° C.for 16 hours. After the reaction is completed, acetone is removed invacuo and the remaining amber oil is collected in quantitative yield.The scheme below illustrates this Synthesis II.

Example 3 Proposed Synthesis of Compounds of Formula (II)

Compounds having the structure of formula (II) may be synthesized asfollows:

A 300 ml bomb is charged with resorcinol (5 g, 48 mmol) and glycidylhexadecyl ether (28.6 g, 96 mmol). To this, acetone (150 ml) is added,the vessel sealed, and the mixture heated to 80° C. for 16 hours. Afterthis first addition, the material is isolated and dried under vacuum.The alcohol moieties created by the epoxide ring opening is used asinitiators in an ethylene oxide polymerization to create a hydrophilicportions on the surfactant, under standard ethylene oxide polymerizationconditions. The scheme below illustrates this Synthesis III:

Example 4 Proposed Synthesis of Compounds of Formula (II)

Compounds having the structure of formula (III) may be synthesized asfollows:

A 300 ml bomb is charged with resorcinol (5 g, 48 mmol) and glycidylhexadecyl ether (14.3 g, 48 mmol). To this, acetone (150 ml) is added,the vessel sealed, and the mixture heated to 80° C. for 16 hours. Afterthis first addition, the material is isolated and dried under vacuum.The alcohol moieties created by the epoxide ring opening is used in thenext reaction to add hydrophilic portions to the molecule. Compound 1 isdissolved in acetone and heated to 80° C. to complete the reactionwithout the need for an ethylene oxide polymerization. The scheme belowillustrates this Synthesis IV.

Example 5 Critical Micelle Concentration

Critical micelle concentration (CMC) is an important metric withsurfactant systems. It is defined as the minimum surfactantconcentration that will form micelles. Below this amount, the moleculesexist only in a non-aggregated form. Additionally, this number alsorepresents the constant concentration of monomeric molecules insolution. Effectively, it describes a lower limit to usage and is a goodfirst approximation to formulation content.

A series of aqueous surfactant dilutions were prepared in deionizedwater with concentrations between 20 μM and 200 mM. The water surfacetension at 22° C. was measured on a KSV 702 tensiometer using the DuNouy ring method. Measured surface tensions were plotted againstconcentration and linear regression analysis was used to find theinflection point denoting the critical micelle concentration (CMC) ofthe surfactant. For testing at higher or lower pH conditions, 0.1 Mbuffer solutions were used. Citric acid buffer was used to stabilize pH3 while sodium bicarbonate was used for a pH 10 buffer.

FIG. 1 illustrates examples of critical micelle concentration of acompound of formula shown below, termed R1 on the graphs below. R1 is aspecies of a compound of formula (I). FIG. 1 also illustrates examplesof critical micelle concentration of a compound of formula shown below,termed R2 on the graphs below.

FIG. 2 shows a plot of CMC as a function of pH for two molecules, R1(shown above) and a compound of formula (V), termed R2 in the graphsbelow. R2 is a species of a compound of formula (II).

Example 6 Emulsion Stability for Oil Flow Behavior

In order to test the capabilities of the surfactants in emulsifying andtransporting heavy crude oils, the viscosity was measured with variousadditions of surfactant solution on a Brookfield viscometer at 22° C.Compounds of formula (VI), designated as R1, and compounds of formula(VII), designated as R2, were tested. Using a LV3 type spindle at 40RPM, the diluted bitumen (residual toluene mixed with bitumen)demonstrated a viscosity of approximately 2000 cP. This diluted bitumenwas then mixed with multiple ratios of a 1 wt % solution of R1 or R2 indeionized water with the pH adjusted to 9 for emulsion activity. FIG. 3illustrates the results of these tests, showing the viscosity of dilutedbitumen as a function of surfactant solution addition.

FIG. 3 demonstrates that incorporation of an aqueous solution ofsurfactant can dramatically decrease the viscosity of diluted bitumen.As shown in FIG. 3, the addition of more than 50 vol % of a diluteaqueous solution of R1 or R2 decreases the bitumen viscosity by nearlyone thousand times. The energy savings of such a system are significant,but the concomitant increase in flowrate enables much higher throughputand residence time in a pipeline.

EQUIVALENTS

While specific embodiments of the subject invention have been discussed,the above specification is illustrative and not restrictive. Manyvariations of the invention will become apparent to those skilled in theart upon review of this specification. Unless otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth herein areapproximations that can vary depending upon the desired propertiessought to be obtained by the present invention.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

1. A compound having the formula:

wherein Ar is a substituted or unsubstituted aryl, arylalkyl orheteroaryl group; p is 1 or 2; m and n are independently 0, 1, 2, 3, 4,or 5; each G₁ and G₂ are independently absent, O, S, NR₂, (CO)O, O(CO),CO, CONR₂, or NR₂CO; each R₂ is independently H or a lower alkyl; eachG₃ is absent, (CH₂)_(q) or G₁; q is 1, 2, 3, 4 or 5; R is a hydrophilicgroup; R₁ is a saturated or unsaturated hydrophobic aliphatic group;wherein when p is 1, Ar is substituted by OH, SH or NH₂; and whereinwhen at least one G₂ is absent, G₁ is other than O.
 2. The compound ofclaim 1 wherein Ar is a substituted or unsubstituted phenyl group. 3.The compound of claim 2 wherein p is
 2. 4. The compound of claim 3wherein each R is independently a COOH or a hydrophilic polymer.
 5. Thecompound of claim 4 wherein each R is independently a polyethyleneglycol or a polypropyleneoxide.
 6. The compound of claim 4 wherein eachR₁ is independently C₅ to C₁₈ alkyl, alkenyl or alkadienyl.
 7. Thecompound of claim 6 wherein each R₁ is a straight chain C₅ to C₁₈ alkyl.8. The compound of claim 7 wherein each G₁ is independently O or OCO. 9.The compound of claim 8 wherein each G₂ is independently O or OCO. 10.The compound of claim 9 wherein each G₁ and G₂ are O.
 11. The compoundof claim 10 wherein each R is independently a polyethylene glycol. 12.The compound having the formula:

wherein R₅ is a hydrophilic group; and R₄ is a saturated or unsaturatedhydrophobic aliphatic group.
 13. A compound of claim 1, having theformula:

wherein G₁ is S, NR₂, (CO)O, O(CO), CO, CONR₂, and NR₂CO; each R₂ isindependently H or a lower alkyl; R₁ is a saturated or unsaturatedhydrophobic aliphatic group; R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ are eachindependently H, OH, halogen, C1-C5 alkyl, C1-C5 alkoxy, aC₃-C₇-cycloalkyl group, a phenyl group optionally substituted byhydroxyl, halogen, lower alkyl or lower alkoxy; or Fragment I having theformula below:

wherein at least one of R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ is selected fromFragment I or OH; or a salt thereof.
 14. The compound of claim 13wherein one of R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ is Fragment I.
 15. Thecompound of claim 13 wherein m is
 1. 16. The compound of claim 13wherein each R₁ is independently a C₅ to C₁₈ alkyl, alkenyl oralkadienyl.
 17. The compound of claim 13 wherein each R₁ isindependently a straight chain C₅ to C₁₈ alkyl.
 18. The compound ofclaim 13 wherein G₁ is OCO.
 19. A compound claim 1 having the formula:

wherein m and R₁ are as defined above.
 20. A method for extracting oilfrom an oil mixture comprising: (a) adding a compound of claim 1 to anoil mixture, and (b) collecting the oil.
 21. The method of claim 20wherein the oil mixture comprises oil sands, wherein said method furthercomprises adding water to the mixture.
 22. The method of claim 20wherein the oil mixture is a waterborne oil slick.
 23. The method ofclaim 20 wherein the oil mixture formed by step (a) is transported via apipeline.
 24. The method of claim 20 wherein step (a) occurs in an oilwell to enhance oil recovery.
 25. A method of degreasing machinery usedin oil or bitumen production comprising cleaning the machinery with acomposition comprising a compound of claim
 1. 26. A method of removingwater and associated salts from oil, comprising: (a) contacting the oilwith a compound of claim 1, and (b) separating the water from the oil.